Synthesis, spectroscopic properties, and electrochemistry of heteroleptic rare earth double-decker complexes with phthalocyaninato and meso-tetrakis (4-chlorophenyl)porphyrinato ligands

Vibrational spectroscopic characteristics of phthalocyanine and naphthalocyanine in sandwich‐type phthalocyaninato and porphyrinato rare earth complexes. Part 11—Raman spectroscopic characteristics of phthalocyanine in mixed [tetrakis(4‐chlorophenyl)porphyrinato](phthalocyaninato) rare earth double‐deckers

“…Both IR and single-crystal structure analysis suggest that the hole for the double-deckers M III (TClPP)(Pc) is mainly localized on the phthalocyanine ring on the vibrational timescale whereas for Ce(TClPP)(Pc) both macrocycles exist as dianions. 37 Therefore, the availability of the whole series of rare earth double-decker complexes with mixed tetrakis(4-chlorophenyl)porphyrin and phthalocyanine ligands here also provides a good chance to compare the Raman vibrational characteristics of phthalocyanine monoanion radical Pc ž and phthalocyanine dianion Pc 2 .…”

“…This was confirmed by the fact that the mutual exclusion rule was not obeyed between the Raman and IR spectra of M(TClPP)(Pc), several phthalocyanine-related Raman frequencies being simultaneously active in the IR spectra. 37 As detailed below from theoretical expectations, for the C 4v symmetric phthalocyanine metal fragment M(Pc) containing 57 atoms, there are only 22 A 1 totally symmetric fundamental vibrations active in the spontaneous Raman spectra, although the fragment M(Pc) contains a large number of atoms and thus possesses many possible normal vibrational modes. In the resonance Raman scattering, a number of new wavenumbers could be attributed to the related 22B 1 , 20B 2 and 41E type in view of the Herzberg-Teller mechanism.…”

Nanoscale Hollow Spheres of an Amphiphilic Mixed (Phthalocyaninato)(porphyrinato)europium Double‐Decker Complex

“…As revealed, these five double-decker complexes, regardless of the number and location of hydroxy groups at the meso-attached phenyl substituents of the porphyrin ring, dissolved in THF, show just the same features in their electronic absorption spectra, revealing the nonaggregated molecular spectroscopic nature of all five compounds including 1 in THF. In line with the neutral analogues with trivalent central metal ions, M III -(Pc)(TClPP) [M = Y, La-Lu except Ce and Pm; TClPP = 5,10,15,20-tetrakis(4-chlorophenyl)porphyrinate] [14] and M III -(Pc)(TPP) (M = La, Pr, Nd, Eu, Gd, Er, Lu, and Y; TPP = 5,10,15,20-tetraphenylporphyrinate), [15a,15b] the absorptions of double-decker 1 at about 320 and 406 nm can be attributed to the phthalocyanine and porphyrin Soret bands, respectively, whereas the absorption bands at 473 and 1008 nm are due to the electronic transitions involving the semioccupied orbital, which has higher phthalocyanine character. An additional characteristic near-IR band for the π-radical anion of trivalent europium double-deckers around 1350 nm can also be observed for the whole series, which confirms the neutral nature of 1-5.…”

“…An additional characteristic near-IR band for the π-radical anion of trivalent europium double-deckers around 1350 nm can also be observed for the whole series, which confirms the neutral nature of 1-5. [14,15] In a similar manner, the absorptions for 2-5 are also assigned. The electronic absorption spectra of 1 together with those of 2-5 in water were also recorded and are given in Figure 2 and Figure S3 (Supporting Information), respectively.…”

Sandwich complexes of yttrium, neodymium, gadolinium, and dysprosium with meso-trans-di(hexadecyl)-tetrabenzoporphyrin and phthalocyanine fragments. Synthesis and spectral properties

“…At present there are numerous methods of synthesis of sandwich lanthanide complexes containing phthalocyanine and porphyrin molecules [6][7][8][9][10]. However, the information about the structure of such complexes containing phthalocyanine and tetrabenzoporphyrin molecules is very limited [11,12], and the information on the structures that combine the meso-trans-dialkyltetrabenzoporphyrin and phthalocyanine fragments has not been found in the literature.…”